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Metal–ligand cluster ions are structurally characterized by means of gas-phase infrared multiple photon dissociation spectroscopy. The mass-selected complexes consist of one or two metal cations M3+ (M = Al, Fe, or Ru) and two to five anionic bidentate acetylacetonate ligands. Experimental IR spectra are compared with different density functional theory calculations, namely, PBE/TZVP, B3LYP/6-31G*, and M06/6-31+G**. Frequency analysis was also performed at different levels, namely, scaled static harmonic and unscaled static anharmonic, or with ab initio molecular dynamics simulations at the PBE/TZVP level. All methods lead to simulated spectra that fit rather well with experimental data, and the spectral red shifts of several main bands, in the 1200 cm−1–1800 cm−1 range, are sensitive to the strength of the metal–ligand interaction and to the spin state of the ion. Due to the rigidity of those complexes, first principles molecular dynamics calculations provide spectra similar to that produced by static calculations that are already able to catch the main spectral signatures using harmonic calculations at the B3LYP/6-31G* level. [ABSTRACT FROM AUTHOR]

L'immersion des civelles (Anguilla anguilla L.) dans une solution hyperosmotique (5 % de chlorure de sodium) pendant 3'30 puis dans une solution contenant 1 % de chlorhydrate de tetracycline (CHTC) ou 2 % de fluorescéine (DCAF) pendant encore 3'30, entraîne une accélération de la vitesse d'entrée de ces deux marqueurs vitaux dans l'organisme des poissons et un marquage rapide des organes calcifiés (vertèbres et otolithes). Des résultats similaires sont obtenus en plaçant les civelles dans une solution contenant à la fois 5 % de chlorure de sodium et 1 % de CHTC ou 2 % de DCAF pendant 3'30. Le choc osmotique est proposé comme une avancée technique pour le marquage vital en masse des larves, des alevins et des stades juvéniles car il permet d'abaisser considérablement le temps de contact nécessaire entre les poissons et la solution de fluoromarqueur. Nous présentons une application de cette technique pour le marquage de 500 kg de civelles avec de la tetracycline. La réalisation de cette manipulation a demandé une journée et demie de travail à 5 personnes. Les résultats obtenus sont de très bonne qualité puisque l'on obtient 100 % de spécimens marqués dont 70 % le sont fortement. Il est donc possible de marquer une grande quantité de civelles dans un laps de temps réduit. Le problème de la reconnaissance in situ des animaux ainsi marqués est discuté.

Experimental and theoretical gas-phase studies of several noncovalent complexes of elementary molecules of biological interest are presented. The comparison provides a test of the validity of the employed methods.

Summary: Background: Topical photodynamic therapy (PDT) using methyl aminolaevulinate is a noninvasive treatment option suitable to treat clinical and subclinical actinic keratosis (AK) over a large area (field cancerization). The most widely used, conventional protocol in Europe includes illumination with a red‐light lamp. This illumination commonly causes pain, and patients often cannot complete the treatment. Objectives: The aims of this paper are twofold. The first aim is to introduce a novel protocol, the Phosistos protocol (P‐PDT), which includes illumination with a fabric‐based biophotonic device. The second and major aim is to assess the noninferiority, in terms of efficacy for PDT of AK, of P‐PDT compared with the conventional protocol (C‐PDT). Methods: A randomized, controlled, multicentre, intraindividual clinical study was conducted. Forty‐six patients with grade I–II AK of the forehead and scalp were treated with P‐PDT on one area (280 AK lesions) and with C‐PDT on the contralateral area (280 AK lesions). The primary end point was the lesion complete response (CR) rate at 3 months, with an absolute noninferiority margin of −10%. Secondary end points included pain scores, incidence of adverse effects and cosmetic outcome. Results: Three months following treatment, the lesion CR rate of P‐PDT was noninferior to that of C‐PDT (79·3% vs. 80·7%, respectively; absolute difference −1·6%; one‐sided 95% confidence interval −4·5% to infinity). The noninferiority of P‐PDT to C‐PDT in terms of the lesion CR rate remained at the 6‐month follow‐up (94·2% vs. 94·9%, respectively; absolute difference −0·6%; one‐sided 95% confidence interval −2·7% to infinity). Moreover, the pain score at the end of illumination was significantly lower for P‐PDT than for C‐PDT (mean ± SD 0·3 ± 0·6 vs. 7·4 ± 2·3; P < 0·001). Conclusions: P‐PDT is noninferior to C‐PDT in terms of efficacy for treating AK of the forehead and scalp and resulted in much lower pain scores and fewer adverse effects. What's already known about this topic? Topical photodynamic therapy using methyl aminolaevulinate is effective for treating actinic keratosis.In Europe, the conventional protocol involves illumination with a red‐light lamp. Unfortunately, pain is often experienced by patients undergoing this protocol.An alternative protocol that uses daylight illumination has recently been shown to be as effective as the conventional protocol while being nearly painless. However, this alternative protocol can be conducted only in suitable weather conditions. What does this study add? The Phosistos protocol is demonstrated to be as effective as the conventional protocol, nearly as painless as the daylight protocols and suitable year round for treatment of actinic keratosis. Plain language summary available online Linked Comment: Gilaberte. Br J Dermatol 2020; 182:11–12. [ABSTRACT FROM AUTHOR]

The gas-phase conformation of the intact (parent) unprotected RGD- peptide anion has been investigated using a combination of anion photoelectron spectroscopy and quantum chemistry calculations of its low-energy stable structures. The experimentally observed RGD- species correspond to a conformation in which the guanidinium group is protonated, the C-terminus is neutral, the aspartic acid carboxyl is deprotonated, and the anion’s excess electron orbital is localized on the protonated guanidinium. This structure is reminiscent of the RGD loop, which is the peptide motif recognized by trans-membrane integrins. The parent RGD- radical anion was generated using a unique infrared desorption-photoemission-helium jet ion source, whose ability to produce radical anions of peptides may also have analytical mass spectrometric implications. [ABSTRACT FROM AUTHOR]

Examines the coupling between the dipole bound and valence electronic states of the nitromethane anion. Use of Rydberg electron spectroscopy for the study; Comparison of the solvation behavior of nitromethane anion with acetonitrile anion; Isolation of dipole bound state from the resonance arising from excess electron occupation in the molecular orbital.

Summary: Background: Photodynamic therapy (PDT) is an effective treatment for actinic keratosis (AK), particularly for patients with large areas of field cancerization. Among the approved protocols in Europe, the most widely used requires irradiation with the Aktilite CL 128 lamp. However, pain during irradiation and the suboptimal adaptability of the lamp relative to the treatment area are two limiting factors of this protocol. To overcome these limits, a new protocol (referred to as the Flexitheralight protocol) involving irradiation with a light‐emitting, fabric‐based device was developed. Objectives: This paper aims to assess the noninferiority, in terms of PDT efficacy for treating AK, of the Flexitheralight protocol compared with the conventional protocol, which requires irradiation with the Aktilite CL 128 lamp. Methods: A monocentric, randomized, controlled, phase II clinical study was performed. Twenty‐five patients with grade I–II AKs of the forehead and scalp were treated with methyl aminolaevulinate PDT in two symmetrical areas. One area was treated with the conventional protocol (n = 154 AKs), whereas the other area was treated with the Flexitheralight protocol (n = 156 AKs). The primary end‐point was the lesion complete response (CR) rate at 3 months (an absolute noninferiority margin of –10% was used). The secondary end‐points included patient‐reported pain at the end of the irradiation. Results: At 3 months, the lesion CR rate with the Flexitheralight protocol was noninferior to that obtained with the conventional protocol (66·0% vs. 59·1%, respectively; absolute difference, 6·9%; 95% confidence interval –0·6% to 14·5%). Patient‐reported pain was significantly lower with the Flexitheralight protocol than with the conventional protocol (mean ± SD: 0·4 ± 0·6 vs. 5·0 ± 2·6; P < 0·0001). Conclusions: The Flexitheralight protocol is noninferior in terms of efficacy and superior in terms of tolerability to the conventional protocol for treating AKs of the forehead and scalp. What's already known about this topic? Methyl aminolaevulinate photodynamic therapy (PDT) is an effective and noninvasive treatment for actinic keratosis (AK).Treatment‐associated pain is frequently experienced by patients treated with the conventional protocol, which requires irradiation with the Aktilite CL 128 lamp.PDT using daylight as the activating light source has been confirmed as equally effective and less painful than the conventional protocol, but it cannot be performed in all weather conditions. What does this study add? This study demonstrates that the Flexitheralight protocol, which can be performed in all weather conditions, is equally effective as the conventional PDT protocol for AK and is a less painful technique. Linked Comment:Morton. Br J Dermatol 2019; 180:703–704. Respond to this article Plain language summary available online [ABSTRACT FROM AUTHOR]

A study of electron attachment properties of a series of saturated disulfides: dimethyl disulfide, diethyl disulfide and dipropyl disulfide, by Rydberg electron-transfer spectroscopy (RETS), negative ion photoelectron spectroscopy (NIPES) and quantum chemistry calculation is presented. Both RETS and NIPES show that the valence anions of these disulfides are stable.

Various hydroxypyridine derivatives are endogenous or synthetic photosensitizers which could contribute to solar radiation damage. The study of their excited states could lead to a better understanding of their action mechanisms. We present here the ultraviolet (UV) spectra of the protonated 2-, 3- and 4-hydroxypyridine. These spectra were obtained with an experimental device coupling an electrospray ion source with a cold quadrupole ion trap and a time of flight mass spectrometer. They display well resolved vibrational structures, with a clear influence of the position of the OH group. These results are interpreted with excited states calculations at the coupled cluster CC2 level. [ABSTRACT FROM AUTHOR]

BackgroundNeonatal jaundice is a common condition occurring in 60%-80% of all healthy-term and late-preterm neonates. In the majority of cases, neonatal jaundice resolves spontaneously and causes no harm; however, in some neonates, significant hyperbilirubinemia can develop and lead to kernicterus jaundice, a serious neurological disease. Phototherapy (PT) is the preferred treatment for jaundice; however, to be effective, PT devices need to have a broad light emission surface to generate no or little heat and to provide an optimal wavelength and light intensity (420-490 nm and ≥30 µW/cm²/nm, respectively). ObjectiveThis study aimed to investigate the feasibility, safety, and level of satisfaction of parents and health care teams with the BUBOlight device, an innovative alternative to conventional hospital PT, in which luminous textiles have been incorporated in a sleeping bag. MethodsThis interventional, exploratory, simple group, nonrandomized, single-center trial will be conducted at Lille Hospital. In total, 10-15 neonates and their parents will be included to obtain evaluable data from 10 parent-neonate pairs. Neonates weighing more than 2500 g at birth and born with ≥37 weeks of amenorrhea that required PT in accordance with the guidelines of the National Institute For Health and Clinical Excellence will receive one 4-hour session of illumination. Total serum bilirubin and transcutaneous bilirubin levels were obtained at the start and 2 hours after the end of PT. Cutaneous and rectal temperatures, heart rate, and oxygen saturation will be measured at the beginning and during PT. The number of subjects is therefore not calculated on the basis of statistical assumptions. We aim to obtain a minimum proportion of 90% (ie, 9 of 10) of the neonates included, who have been able to undergo 4-hour PT without unacceptable and unexpected toxicities. We will calculate the mean, median, quartiles, minimum and maximum values of the quantitative parameters, and the frequency of the qualitative parameters. The rate of patients with no unacceptable and unexpected toxicities (ie, the primary endpoint) will be calculated. ResultsThe first patient is expected to be enrolled at the end of 2020, and clinical investigations are intended for up to June 2021. The final results of this study are expected to be available at the end of 2021. ConclusionsOur findings will provide insights into the safety and feasibility of a new PT device based on light-emitting fabrics for the treatment of newborn jaundice. This new system, if proven effective, will improve the humanization of neonatal care and help avoid mother-child separation. Trial RegistrationClinicalTrials.gov NCT04365998; https://clinicaltrials.gov/ct2/show/NCT04365998 International Registered Report Identifier (IRRID)PRR1-10.2196/24808